Method for making a polymer semiconductor and article



3,083,125 METHOD FDR MAKING A POLYMER SEMI- CONDUCTOR AND ARTICLE Ferdinand Bohlnrann, Beriin-Charlottenburg, Hans Dexheimer, Mainz-Momhach, Otto Fuchs, Hofheim, Taunus, and Hans Kramer, Frankfurt am Main, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormais Meister Lucius & Briining, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed Oct. 17, 1960, Ser. No. 62,836 6 Claims. (Cl. 117-201) This invention relates to semi-conductor devices and to a method of making such devices.

In technical practice semi-conductors are finding a continuously growing interest, for example, in the manufacture of transistors, semi-conductor photo-resistances, semi-conductor photo-elements, semi-conductor resistances, semi-conductor rectifiers and the like. Hitherto for this region of electrotechnics primarily semiconductors having an inorganic basis have been used. In order to extend the application possibilities of semi-conductors,

to simplify their manufacture and for better adaptation of their properties to particular requirements, it is in practice ofgreat interest to employ synthetic semi-conductors having an organic basis. Semi-conductors of organic nature have in addition the advantage of a capacity for wide use asxantistatic agents. The organic substances hitherto used as semi-conductors, such as anthracene, naphthalene, pyrene, and so on, havethe great disadvantage as regards technical application of melting at temperatures that are only slightly elevated, and of being relatively easily volatile. In' addition they have at elevated temperatures the further disadvantage of being more or less soluble in liquid media, which is particularly detrimental in the application of the semi-conductor in high frequency or high potential rectifiers.

The present invention relates to a semi-conductor device, for example, a semi-conductor resistance, rectifier, photo element or transistor, with a semi conducting element consisting of organic semi-conducting compounds and to the use of such compounds in the making of semiconductor devices. According to the invention there are used as organic semi-conducting compounds reaction products of polyynes, of a type known per se, obtained by heating and/or irradiation at a temperature below the melting point, of polyynes of the general formula in which n is a numeral equal to or greater than 2, and R and R are the same or different organic radicals. Of the products obtained by the heating of polyynes those forming in a temperature range which is by 5 to 20 C. below the melting point are in general particularly advantageous for use according to the invention. Regarding the structure and reactivity of polyynes of the above general formula, see, for example, F. Bohlmann, Angewandte Chemie, 69, 82 (1957).

The reaction products to be used according to the invention can be obtained by heating and/ or irradiation of, for example, the following compounds: 4-methyltetradecadiene (4.12) triyne(6.8.l)-one(2) (melting point 38.5 C.) and the dinitrophenylhydrazone thereof (melting at 202 C. with decomposition); tetradecatriyne- (4.6.8)-ene(2)-one(12) (melting point 64 C.) and the paracarboxyphenylhydrazone thereof (melting at and above 170 C. with decomposition); tetradecadiyne (2.4.6)-ene(8)-one(12) (melting point 57.5 C.) and the para-carboxyphenylhydrazone thereof (melting point at and above 170 C.); the transdecatriyne(2.4.6)-ene(8)- acid methyl ester (melting point 61 C.); the trans-octadiyne(2.4)ene(6)-acid methyl ester (melting point 32.5 C.); the 2.2.l3.13-tetramethyl-tetradecatetrayne- 3,083,125. Patented Mar. 26, 1963 2 .7 3.5 .7.9)-ene( 1 1 )-ol( 12) -methy1 ether '(melting point 1 14 to 115 C.); the octadiyne-(2.4)-ene(6)-ol(7) methy1 ether (melting point 43 to 46 C.); octadiyne-(2.4)- one(6) (having a melting point .of -10 C. and aboiling point under 0.5 mm. of mercury of 30 C.) and the 81 C.); l-bromo-decadiyne (4.6)-diene(2.8) (melting point 44.5 C.); l-phenyl-nonatriyne (1.3.5 -ene(7)-ol(9) (melting point 103 C.); l-phenyl-nonatriyne (1.3.5)- ene(7)-al(9) (melting point 75 C.); 1-phenyl-undecatriyne-(l.3.5)-diene(7.9) (melting point 64 C.) and the maleic acid anhydride adduct thereof (melting at 173 C. with decomposition); 3.8-dimethyl-decadiene(2.8)-diyne- (4.6 )-diol (1.10)-diacetate (melting point 70 C.) and the diepoxide thereof (inelting' point 99 C.); 'hexa'diyne (2.4)-dial( 1.6) and the bis-dinitrophenyl hydrazoneth'erei of (melting at 215 to 220 C. with decomposition); bis-f [cyclohexene( 1 -yl( 1 ]-triacetylene (melting point 71 C.); 1.1.8.S-tetraphenyl-octatriyne ".(2.4.6)-diol(1 .8) (melting point 159 C.);'.rl iphenyltriacetylene (melting point 91 to 92 C.); bis['1-oXy-cyclohexy1(1).]-tetraacet ylene (melting point 151 Cg); pentadiynej (2.4) -0,l(1

(melting point '-20 C.); lecyandeca-triyne('4.6f8)-ene (2) (melting point 92 C.-)';"1 carbomethoxy-decatriyne (4.6.8) ne(2) (melting at 165C. with decomposition); bis[l-oxy 2.2.6.6 tetramethylcyclohexyl(1)fl-butadiyn 1 (melting point 173 CIT; 'bis[1-OXy -2.2.6.6 ttrainetliyl cyclohexylfl)j-hexatriyne (melting point 204 C.); bis= E 1'-bron1o-2;2.6.6-tetramethyl-cyclohexyl ('1 T" hexatriyne (melting point 212 to 213 C.); 2.2.9.9-tetramethyldecadiyne (4.6)-diol(3.8) (melting point 86 C.); 3.8- dichloro 2.2.9.9 tetramethyl-decadiyne(4.6) (melting point 164 C.); 2.2.9.9-tetramethy1-decatriyne (3.5.7) (melting point 70 C.); 2.2.17.17-tetramethyl-octadecadiene(3.15)-pentayne (5.7.9.1113) (melting point 130 C.) 2.2.1 1.1 1-tetramethyl-dodecatetrayne (3.5 .7.9) (melting point 99 to 100 C.).

It is of particular advantage to use products that have been obtained by heating and/or irradiation of the following polyynes:

Decadiyne(4,6)diol(1:10) (melting point 46 C.) and the diurethane obtained from decadiyne (4.6)dio1(1.10) and alpha-naphthylisocyanate; the trans-dodecatriyne (4.6.8) ene(10) ol(2) beta anthraquinone carboX- ylic acid ester (melting at 122 to 123 C. with decomposition) and the cis dodecatriyne(4.6.8) (l0) ol(2)- beta-anthraquinone carboxylic acid ester (melting point 121 C.); decatriyne-(2.4.6)-ene(8)-ol(9)-methyl ether (melting point 71 C.); bis[cyclohexene(1)-yl(1)]-tetraacetylene (melting point 127 C.); bis[oxy-methyl]- tetra-acetylene (melting point C.); [l-oxy-cyclohexyl(1)] -triacetylene, bis[1-oXy-cyclohexyl(1)] hexaacetylene; 2.2.15.15 tetramethylhexadecahexayne(3.5. 7.9.11.13) (melting point C.); 2.2.17.17-tetramethyl-octadecaheptayne (3.5.7.9.1-'1.'13.15) (melting point above C.); octadecahexayne(4.6.8.10.13.14)-diene- (2.16)-diol (1.18)-diacet-ate.

The conversion products obtained by heating and/or irradiation of polyynes of the above general structure are in general deeply colored and diificultly soluble or insoluble.

For some purposes of application the difiicult solubility or practical insolubility of the conversion products of polyynes may be detrimental because the products for these particular purposes of application cannot be applied in av simple manner'to'a solid substratum, for example, to a metal or aninorganic or organic noncon'ductor, such as quartz or a synthetic plastic material or the like. These production difficulties may easily be avoided .by first preparing a solution of the initial polyyne of the greatest possible concentratiom using an easily volatile solvent, .for example, acetone, by applying this solution to a solid substratum andthen evaporating the solvent. The coated product obtained is then subjected to heat and/or irradiation in order to convert the polyyne layer into the required product of semi-con ducting character. V.

' The following example serves to illustrate the invention butit is not intended to limit it thereto.

4.63 grams of a pale violet polyyne of the general formulagiven above in which n=2 andu'c't is seen from the following table:

10.; sol 100; 150 200 not The unreacted initial polyyne passed into solution in the extraction and could be recovered by evaporation of the acetone.

We claim:

1. A method of making a semi-conductor device which comprises applying to a solid substratum a polyyne of the formula in which n represents an integer of at least 2 and R and R indicate organic radicals and heating .said 'polyyne to a temperature within the range of 5 to 20 C. below its melting point.

2. A method as defined in claim 1 wherein the polyyne is applied to the substratum in the form of a solution in a volatile solvent and the volatile solvent is subsequently volatilized.

'3. A method as defined in claim 1 wherein the polyyne is heated by irradiation.

'4. A product produced according to the method of claim 1.

5.. A method of making a semi-conductor device which comprises applying to a solid substratum a polyyne oftheformula a a R --(CEC),,'R in' which n represents an integer of at least 2 and R and R indicate the same organic radicals and heating said polyyne to a temperature withinthe range of 5 to 2()" C. below its melting point. V

6. A method of making a semi-conductor device which-comprises applying tosa solid substratum a polyyne of the formula i R1(CEC) '-R in which 'n represents'aninte'ger of at least 2 and .R and R findieate different organic radicals and heating said polyyne to ai'temperature' within the range of 5 to 2 0' C. below its melting point.

References Cited in the file of this patent FOREIGN PATENTS Austria a Aug. 11, 1958 

1. A METHOD OF MAKING A SEMI-CONDUCTOR DEVICE WHICH COMPRISES APPLYING TO A SOLID SUBSTRATUM A POLYYNE OF THE FORMULA 